The present invention relates to methods of producing polymeric compounds, in particular using radiation curing such ultraviolet or thermal radiation, or chemical curing or electron beam initiated curing. Certain compounds which form polymers under the influence of u.v. light form a further aspect of the invention, as well as to polymers, coatings and adhesives obtained thereby.
The polymerisation of diallyamines using free radical initiation is known, for example from Solomon et al., J. Macromol. Sci.- Rev Macromol. Chem. c15 (1) 143-164 (1976). Free radical initiation of polymerisation requires quite extreme reaction conditions which can be generated only in production plants etc. It is not suitable for situations where in situ polymerisation is required.
Other cyclpolymerisation reactions are discussed by C. D. McLean et al., J. Macromol. Sci.-Chem., A10 (5), pp857-873 (1976). Yet further reactions are described in WO 97/16504, WO97/16472 where such reactions are used in a specialised way in the production of liquid crystal compounds.
The applicants have found that a broad range of compounds with at least two appropriately positioned multiple bonds and in particular double bonds may be activated by the presence of an electron withdrawing group, in particular where the electron withdrawing group is at a position which is alpha, beta or gamma to one or both of the double bonds to make them readily polymerisable under the influence of inter alia radiation. The term xe2x80x9creadily polymerisablexe2x80x9d means that the compounds will undergo polymerisation under moderate conditions of temperature and pressure (for example at room temperature and atmospheric pressure) in the presence of radiation and an initiator, in a period of less than 24 hours.
Polymeric compounds obtained therefrom include cyclic rings. These have many advantageous properties. In particular, the invention can be used to generate products such as adhesives (see copending British Patent application No 9816169.8), coatings, network polymers or conducting polymers (see copending British Patent Application No. 9816171.0) depending upon the other aspects of the structure of the starting materials.
In its broadest aspect, the invention provides a method for producing a polymeric material, said method comprising subjecting a starting material which includes two double bonds which are activated so that they will take part in a polymerisation reaction and wherein the double bonds are sufficiently close together to ensure that cyclopolymerisation will preferentially occur; to suitable conditions under which said polymerisation reaction will occur, provided that the starting material is other than triallyamine hydrochloride.
Specifically, the invention provides a method for producing a polymeric material, said method comprising subjecting a starting material which comprises a group of sub-formula (I) 
where
R1 is CRa where Ra is hydrogen of alkyl, and R6 is a bond, or R1 and R6 together form an electron withdrawing group;
R2 and R3 are independently selected from (CR7R8)n, or a group CR9R10, CR7R8CR9R10 or CR9R10CR7R8 where n is 0, 1 or 2, R7 and R8 are independently selected from hydrogen or alkyl, and either one of R9 or R10 is hydrogen and the other is an electron withdrawing group, or R9 and R10 together form an electron withdrawing group, and
R4 and R5 are independently selected from CH or CR11 where R11 is an electron withdrawing group;
the dotted lines indicate the presence or absence of a bond, and X1 is a group CX2X3 where the dotted line bond to which it is attached is absent and a group CX2 where the dotted line bond to which it is attached is present, Y1 is a group CY2Y3 where the dotted line bond to which it is attached is absent and a group CY2 where the dotted line bond to which it is attached is present, and X2, X3, Y2 and Y3 are independently selected from hydrogen and fluorine;
provided that at least one of (a) R1 and R6 or (b) R2 and R3 or (c) R4 and R5 includes an electron withdrawing group which is able to activate a cyclopolymerisation reaction; to suitable conditions under which a cyclopolymerisation reaction will occur, subject to the following further provisos:
(i) that the starting material is other than triallyamine hydrochloride;
(ii) that when R1 and R6 together form the sole electron withdrawing group and R1 is a group N+R12 (Zmxe2x88x92)1/m, where R12 is hydrogen or hydrocarbyl, Z is an anion of charge m and R6 is a bond, said conditions are subjecting the compound to radiation in the substantial absence of a solvent or sulphur dioxide gas; and
(iii) that where R1 and R6 together form the sole electron withdrawing group and R1 is CH and R6 is OC(O), then the compound does not further contain a mesogenic group, or contains at least one further group of sub-formula (I).
As used herein, the expression xe2x80x9cin the substantial absence of solventxe2x80x9d means that there is either no solvent present or there is insufficient solvent present to completely dissolve the reagents, although a small amount of a diluent may be present to allow the reagents to flow.
Conditions under which polymerisation will occur include the influence of radiation or an electron beam, or in the presence of a chemical initiator. Radiation or electron beam induced polymerisation is suitably effected in the substantial absence of a solvent.
In particular X1 and Y1 are groups CX2X3 and CY2Y3 respectively and the dotted lines represent an absence of a bond. Thus preferred compounds are those of sub-formula (IA) 
where R1, R2, R3, R4, R5, R6, X2, X3, Y2 and Y3 are as defined above. One or more such starting materials may be polymerised together. When more than one starting material is used, a copolymer will result.
When the dotted bonds in sub formula (I) are present, the resulting polymer will comprise polyacetylene chains. This can lead to a conjugated system and consequently a conducting polymer.
Suitably there are no more than five atoms in between or linking the double bonds in the starting material so that when the cyclopolymerisation takes place, for example as illustrated hereinafter in FIG. 1, the size of the rings formed does not exceed 7. Preferably, there are from 3 to 5 atoms in between the double bonds.
Suitably the starting material is one which will cyclopolymerise in the sort of conditions used in polymer production. This may comprise the application of radiation such as uv or thermal radiation, where necessary in the presence of a photoinitiator, by the application of other sorts of initiator such as chemical initiators, or by initiation using an electron beam. The expression xe2x80x9cchemical initiatorxe2x80x9d as used herein refers to compounds which can initiate polymerisation such as free radical initiators and ion initiators such as cationic or anionic initiators as are understood in the art.
Preferably, the starting materials polymerise under the influence of ultraviolet or thermal radiation, preferably ultraviolet radiation. Cyclopolymerisation may take place either spontaneously or in the presence of a suitable initiator. Examples of suitable initiators include 2,2xe2x80x2-azobisisobutyronitrile (AIBN), aromatic ketones such as benzophenones in particular acetophenone; chlorinated acetophenones such as di- or tri-chloroacetophenone; dialkoxyacetophenones such as dimethoxyacetophenones (sold under the Trade name xe2x80x9cIrgacure 651xe2x80x9d); dialkylhydroxyacetophenones such as dimethylhydroxyacetophenone (sold under the Trade name xe2x80x9cDarocure 1173xe2x80x9d); substituted dialkylhydroxyacetophenone alkyl ethers such compounds of formula 
where Ry is alkyl and in particular 2,2-dimethylethyl, Rx is hydroxy or halogen such as chloro, and Rp and Rq are independently selected from alkyl or halogen such as chloro (examples of which are sold under the Trade names xe2x80x9cDarocure 1116xe2x80x9d and xe2x80x9cTrigonal P1xe2x80x9d); 1-benzoylcyclohexanol-2 (sold under the Trade name xe2x80x9cIrgacure 184xe2x80x9d); benzoin or derivatives such as benzoin acetate, benzoin alkyl ethers in particular benzoin butyl ether, dialkoxybenzoins such as dimethoxybenzoin or deoxybenzoin; dibenzyl ketone; acyloxime esters such as methyl or ethyl esters of acyloxime (sold under the trade name xe2x80x9cQuantaqure PDOxe2x80x9d); acylphosphine oxides, acylphosphonates such as dialkylacylphosphonate, ketosulphides for example of formula 
where Rz is alkyl and Ar is an aryl group; dibenzoyl disulphides such as 4,4xe2x80x2-dialkylbenzoyldisulphide; diphenyldithiocarbonate; benzophenone; 4,4xe2x80x2-bis(N,N-dialkylamino)benzophenone; fluorenone; thioxanthone; benzil; or a compound of formula 
where Ar is an aryl group such as phenyl and Rz is alkyl such as methyl (sold under the trade name xe2x80x9cSpeedcure BMDSxe2x80x9d)
As used herein, the term xe2x80x9calkylxe2x80x9d refers to straight or branched chain alkyl groups, suitably containing up to 20 and preferably up to 6 carbon atoms. The term xe2x80x9calkenylxe2x80x9d and xe2x80x9calkynylxe2x80x9d refer to unsaturated straight or branched chains which include for example from 2-20 carbon atoms, for example from 2 to 6 carbon atoms. Chains may include one or more double or triple bonds respectively. In addition, the term xe2x80x9carylxe2x80x9d refers to aromatic groups such as phenyl or naphthyl.
The term xe2x80x9chydrocarbylxe2x80x9d refers to any structure comprising carbon and hydrogen atoms. For example, these may be alkyl, alkenyl, alkynyl, aryl such as phenyl or napthyl, arylalkyl, cycloalkyl, cycloalkenyl or cycloalkynyl. Suitably they will contain up to 20 and preferably up to 10 carbon atoms. The term xe2x80x9cheterocylylxe2x80x9d includes aromatic or non-aromatic rings, for example containing from 4 to 20, suitably from 5 to 10 ring atoms, at least one of which is a heteroatom such as oxygen, sulphur or nitrogen. Examples of such groups include furyl, thienyl, pyrrolyl, pyrrolidinyl, imidazolyl, triazolyl, thiazolyl, tetrazolyl, oxazolyl, isoxazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl, iosquinolinyl, quinoxalinyl, benzthiazolyl, benzoxazolyl, benzothienyl or benzofuryl.
The term xe2x80x9cfunctional groupxe2x80x9d refers to reactive groups such as halo, cyano, nitro, oxo, C(O)nRa, ORa, S(O)tRa, NRbRc, OC(O)NRbRc, C(O)NRbRc, OC(O)NRbRc, xe2x80x94NR7C(O)nR6, xe2x80x94NRaCONRbRc, xe2x80x94Cxe2x95x90NOR , xe2x80x94Nxe2x95x90CRbRc, S(O)tNRbRc, C(S)nRa, C(S)ORa, C(S)NRbRc or xe2x80x94NRbS(O)tRa where Ra, Rb and Rc are independently selected from hydrogen or optionally substituted hydrocarbyl, or Rb and Rc together form an optionally substituted ring which optionally contains further heteroatoms such as S(O)s, oxygen and nitrogen, n is an integer of 1 or 2, t is 0 or an integer of 1-3. In particular the functional groups are groups such as halo, cyano, nitro, oxo, C(O)nRa, ORa, S(O)tRa, NRbRc, OC(O)NRbRc, C(O)NRbRc, OC(O)NRbRc, xe2x80x94NR7C(O)nR6, xe2x80x94NRaCONRbRc, xe2x80x94NRaCSNRbRc, xe2x80x94Cxe2x95x90NORa, xe2x80x94Nxe2x95x90CRbRc, S(O)tNRbRc, or xe2x80x94NRbS(O)tRa where Ra, Rb and Rc, n and t are as defined above.
The term xe2x80x9cheteroatomxe2x80x9d as used herein refers to non-carbon atoms such as oxygen, nitrogen or sulphur atoms. Where the nitrogen atoms are present, they will generally be present as part of an amino residue so that they will be substituted for example by hydrogen or alkyl.
The term xe2x80x9camidexe2x80x9d is generally understood to refer to a group of formula C(O)NRaRb where Ra and Rb are hydrogen or an optionally substituted hydrocarbyl group. Similarly, the term xe2x80x9csulphonamidexe2x80x9d will refer to a group of formula S(O)2NRaRb.
AS described above, suitable starting materials for use in the method of the invention will comprise a group of sub-formula (I) 
where
X1, X2, Y1 and Y2 are independently selected from hydrogen or fluorine, R1 is CRa where Ra is hydrogen or alkyl, and R6is a bond, or R1 and R6 together form an electron withdrawing group;
R2 and R3 are independently selected from (CR7R8)n, or a group CR9R10, xe2x80x94(CR7R8CR9R10)xe2x80x94 or xe2x80x94(CR9R10CR7R8)xe2x80x94 where n is 0, 1 or 2, R7 and R8 are independently selected from hydrogen or alkyl, and either one of R9 or R10) is hydrogen and the other is an electron withdrawing group, or R9 and R10 together form an electron withdrawing group, and
R4 and R5 are independently selected from CH or CR11 where R11 is an electron withdrawing group;
provided that at least one of (a) R1 and R6 or (b) R2 and R3 or (c) R4 and R5 includes an electron withdrawing group.
The nature of the electron withdrawing group or groups used in any particular case will depend upon its position in relation to the double bond it is required to activate, as well as the nature of any other functional groups within the compound.
In a preferred embodiment, R1 and R6 form an electron withdrawing group. For example, R1 is a heteroatom or a substituted heteroatom which has electron withdrawing properties, for example a group N+R12 (Zmxe2x88x92)1/m, S(O)pR3 , B, P(O)qR14 or Si(R15) where R12, R13, R14 and R15 are independently selected from hydrogen or hydrocarbyl, Z is an anion of charge a, p is 0, 1 or 2, and q is 1; and R6 is a bond: or R1 is a group CH and R6 is a group xe2x80x94C(O)Oxe2x80x94 or xe2x80x94OC(O)xe2x80x94. Most preferably, R1 is a group N+R12 (Zmxe2x88x92)1/m, S(O)pR13, B, P(O)qR14 or Si(R15) where R12, R13, R14 and R15 are independently selected from hydrogen or alkyl in particular C1-3 alkyl, and Z is an anion, preferably a halide. In particular R1 is a group N+R12 (Zmxe2x88x92)1/m, and R6 is a bond.
The nature of the anion Z will affect the properties of the final polymer and in particular, its conductivity, porosity and water permability. Suitable anions for the Z group include halide ions such as fluoride, chloride, bromide or iodide, borides such as boron tetrafluoride; carboxylic acid esters such as those of formula R14C(O)Oxe2x80x94 where R14 is an optionally substituted hydrocarbyl group group such as haloalkyl, in particular trifluoromethyl; and other cationic groups such as mesylate and tosylate. In general, the water permeability of the ultimate polymer will vary as follows:
PF6xe2x88x92 less than BF4xe2x88x92 less than CF3SO3xe2x88x92 less than CF3COOxe2x88x92 less than NO3xe2x88x92 less than SO42xe2x88x92 less than Ixe2x88x92 less than Brxe2x88x92 less than Clxe2x88x92
Other factors which affect the water permeability of the polymer is the nature of any group to which the group of sub-formula (I) is attached. When this contains for example perhaloalkyl substituents such as perfluoroalkyl, it will be largely water impermeable as compared to polymers which have alkylene bridging groups optionally interposed with say oxygen. Examples of such groups are given below.
Most preferably, the combination of R1 and R6 forms an amide group, where R1 is a nitrogen atom and R6 is a carbonyl group. In a further preferred embodiment, R1 and R6 together form a sulphonamide group where R1 is a nitrogen atom and R6 is an S(O)2 group.
Alternatively, where the activation is effected by electron withdrawing groups at a position indicated by R2 or R3, suitable electron withdrawing groups R9 and R10 include nitrile, trifluoromethyl, acyl such as acetyl or nitro, or preferably R9 and R10 together with the carbon atom to which they are attached form a carbonyl group.
Where R11 is an electron withdrawing group, it is suitably acyl such as acetyl, nitrile or nitro.
Preferably X1, X2, Y1 and Y2 are all hydrogen.
Suitable groups Ra include hydrogen or methyl, in particular hydrogen.
A preferred group of the compounds for use in the method of the invention is a compound of structure (II) 
and in particular a compound of formula (IIA) 
where X1, X2, X3, Y1, Y2, Y3, R1, R2, R3, R4, R5, R6 and the dotted bonds are as defined in relation to formula (I) above, r is an integer of 1 or more, and R16 is a bridging group, an optionally substituted hydrocarbyl group, a perhaloalkyl group or an amide, of valency r.
Where in the compound of formula (II) and (IIA), r is 1, compounds can be readily polymerised to form a variety of polymer types depending upon the nature of the group R16 and examples of groups which are commonly found in polymer technology is included below in Table 1. Some may be able to act, for example, as radiation curable adhesives as described in copending British Patent application No 9816169.8.
However, other applications for such polymers obtained using the process of the invention may be found.
Monomers of this type may be represented as structure (III) 
where X1, X2, Y1, Y2, R1, R2, R3, R4, R5 and R6 are as defined in relation to formula (I) above, R16 is an optionally substituted hydrocarbyl group, a perhaloalkyl group or an amide.
Preferably in the compounds of formula (III), as above, R1 and R6 form an electron withdrawing group. Suitably then R2 and R3 are groups (CR7R8) n and R1 and R5 are CH groups. Suitably, in the case of adhesives, R16 comprises a hydrocarbyl group, optionally substituted by a functional group. Preferably R7 includes an unsaturated moiety, such as an aryl or alkenyl group, or a carbonyl substituent.
A class of compounds of formula (III) are those of formula 
where R6 is as defined above, and is in particular an optionally substituted alkyl, alkenyl, alkynyl or aryl group, wherein the optional substituents may be selected from halogen, hydroxy, carboxy or salts thereof or acyloxy. These compounds may be used in the monomer form as adhesive compositions. However, pre-formed polymers obtained by polymerisation of these monomers form an aspect of the present invention.
Alternatively, R16xe2x80x2 in formula (IV) may comprise a perhaloalkyl group, for example of from 1 to 3 carbon atoms such as a perhalomethyl group, in particular perfluoromethyl. Another group for R16xe2x80x2 in formula (IV) is a dialkenyl substituted amide, for example of sub formula (V) 
where R18 and R19 are selected from groups defined above for R2 and R3 in relation to formula (I), and are preferably xe2x80x94CH2xe2x80x94 or xe2x80x94CH2CH2xe2x80x94 groups; and R20 and R21 are selected from groups defined above as R3 and R4 in relation to formula (I) and are preferably xe2x80x94CHxe2x80x94 groups. Such groups would further activate the double bonds and give rise to the possibility of forming cross-linked polymer networks.
Another class of compound of formula (II) is represented by radiation curable compounds of formula (VI) 
where Z and m are as defined above, R22 and R23 are independently selected from hydrogen and hydrocarbyl, such as alkyl and alkenyl, in particular prop-2-enyl or hydroxyethyl.
The invention may also be applied to other sorts of polymers, for example, where in the compounds of formula (II), r is greater than one, polymerisation can result is polymer networks. Particular examples are compounds of formula (II) as defined above, where R16 is a bridging group and r is an integer of 2 or more, for example from 2 to 8 and preferably from 2-4.
On polymerisation of these such compounds, networks are formed whose properties may be selected depending upon the precise nature of the R16 group, the amount of chain terminator present and the polymerisation conditions employed. Polymerisation will occur in accordance with the general scheme set out in FIG. 1 hereinafter.
Suitably r is an integer of from 2 to 6, preferably from 2 to 4. The polymers produced can be useful in a number of different applications including the production of network polymers and those used in thermal management. Such applications are described and claimed in copending British Patent application No. 9816171.0.
Thermal management is the control of optical properties of materials across solar and thermal wavebands (xcx9c0.7-12microns). This control of transmitted, reflected and absorbed radiation gives the potential to design systems that can selectively perform different tasks at different wavelengths. For example use of silver coatings by the glazing industry to limit solar transmission (material transparent at visible wavelengths but reflective across the solar) and thus prevent xe2x80x98greenhousexe2x80x99 heating. Other example could be solar water heaters where the material is transparent at NIR wavelengths but reflective at longer wavelengths. Benefits of thermal management could be in reduced air conditioning/heating costs.
The properties of the polymer obtained in this way will depend upon a variety of factors but will depend very largely on the nature of the group R16.
Suitably R16 will comprise a bridging groups for example as is known in polymer, paint or coating chemistry. These may include straight or branched chain alkyl groups, optionally substituted or interposed with functional groups or siloxane groups such as alkyl siloxanes. Suitable bridging groups include those found in polyethylenes, polypropylenes, nylons, as listed in Table 1.
The length of the bridging group will affect the properties of the polymeric material derived from this. This can be used to design polymers with properties which are best suited to the application. For instance when the bridging group comprises relatively long chains, (for example with in excess of 6 repeat units, for example from 6-20 repeat units), the polymer will have pliable plastic properties. Alternatively, when the bridging group is relatively short, (e.g. less than 6 repeat units) the material will be more brittle.
Another method for producing particular properties arises from the possibility of producing copolymers where another monomeric compound, for example one which is not of formula (I), is mixed with the compound of formula (I) prior to polymerisation. Such monomers are known in the art.
Composites may also be produced by polymerising compounds of formula (I) in the presence of other moieties such as graphite, ethers such as crown ethers or thioethers, phthalocyanines, bipyridyls or liquid crystal compounds, all of which will produce composite polymers with modified properties.
Examples of possible bridging groups R16where r is 2 are groups of sub-formula (VII)
xe2x80x94Z1xe2x80x94(Q1)axe2x80x94(Z2xe2x80x94Q2)bxe2x80x94Z3xe2x80x94xe2x80x83xe2x80x83(VII)
where a and b are independently selected from 0, 1 or 2, z1, Z2 and Z3 are independently selected from a bond, an optionally substituted linear or branched alkyl or alkene chain wherein optionally one or more non-adjacent carbon atoms is replaced with a heteroatom or an amide group, Q1 and Q2 are independently selected from an optionally substituted carbocylic or heterocyclic ring which optionally contains bridging alkyl groups.
Suitable carbocyclic rings for Q1 and Q2include cycloalkyl groups for example from 1 to 20 carbon atoms. Bridged carbocylic ring structures include 1,4-bicyclo[2.2.2] octane, decalin, bicyclo[2.2.1]heptane, cubane, diadamantane, adamantane. Suitable heterocyclic rings include any of the above where one or more non adjacent carbon atoms are replaced by a heteroatom such as oxygen, sulphur or nitrogen (including amino or substituted amino), or a carboxyl or an amide group. Suitable optional substitutents for the groups Q1 and Q2 include one or more groups selected from alkyl, alkeny, alkynyl, aryl, aralkyl such as benzyl, or functional groups as defined above. Substitutents for the groups Q1 and Q2 are oxo and halogen in particular fluorine and chlorine.
Suitable optional substituents for the alkyl and alkene groups Z1, Z2 and Z3 include aryl, aralkyl and functional groups as defined above. Particular substituents include halogen such as fluorine and chlorine, and oxo.
Other sorts of bridging groups R16 include electrically conducting chains, for instance, electrically conducting unsaturated chains such as alkenes or chains incorporating aromatic or heterocyclic rings. For instance, the group R16 may comprise a tetra substituted conducting unit such as a tertathiafulvalene. Thus an example of such a is a compound of formula (VIII) 
where R28, R29, R30 and R31 are each groups of sub-formula (IX) 
where R1, R2, R3, R4, R5 and R6 are as defined in relation to formula (I) above and R24, R25, R26 and R27 are independently selected from groups of sub-formula (II) as given above. In particular R24, R25, R26 and R27 are alkyl groups.
Polymerisation of compounds of formula (III) will give cross-linked networks where the cross-linking occurs through the double bonded units. This will lead to a very stable material with robust physical properties. Once again, varying the length of the spacer groups R24, R25, R26 and R27 will lead to materials with designer properties. For instance when R24, R25, R26 and R27 are relatively long chains, the polymer will have pliable plastic properties. Alternatively, when the chains R24, R25, R26and R27 are relatively short, the material will be more brittle.
Where R1 and R6 together form a group xe2x80x94Nxe2x80x2R7Zxe2x88x92, varying the counter ion Z can also be used to adjust the physical properties of the polymer, such as water retention, porosity or conductivity. Suitably substituted materials will exhibit conducting properties, making them suitable as organic semiconductors for example for use as interconnects for IC chips etc.
Alternatively, a bridging group R16 may comprise a tetra or octa substituted non-linear optic unit such as an optionally substituted porphyrin or phthalocyanine wherein the optional substitutents include hydrocarbyl groups as well as groups of sub formula (I). An example of such a porphyin compound is a compound of formula (X) 
where R24, R25, R26, R27, R28, R29, R30 and R31 are as defined in relation to formula (III) above and R32, R33, R34 and R35 are each independently selected from hydrogen or hydrocarbyl groups; and the compound optionally contains a metal ion within the macrocyclic heterocyclic unit.
An alternative phthalocyanine compound is a compound of formula (XA) 
where R50 through to R65 are independently selected from hydrocarbyl in particular C1-12 alkyl, a group OR68 where R68 is hydrocarbyl in particular butyl, halogen in particular chlorine or a group R24-R28 where R24 and R28 are as defined in relation to formula (III) above, provided that at least two of R50 to R65 are R24-R28 groups, and R66 and R67 are either hydrogen or together comprise a metal ion such as a copper ion.
Preferably in formula (XA), R51, R52, R55, R56, R59, R60, R63 and R64 are halogen and R50, R53, R54, R57, R58, R61, R62 and R65 are independently C1-12 alkyl, C1-12 alkoxy or a group R24-R28 
Polymerisation of a compound of formula (X) or (XA) in accordance with the scheme of FIG. 1, for example by photopolymerisation will provide a cross linked network polymer where the cross linking occurs through the diene units for example as either quaternery ammonium salts or amides depending upon the particular nature of the groups R1 and R6 present in the R28, R29, R30 and R31 units. Again this can produce a very stable network or elastomeric material with robust physical properties. In addition to conductivity, these polymers will be capable of exhibiting third order polarisabilities and be suitable for applications which employ the Kerr effect. These properties can be affected or moderated when metals or metal ions are inserted into the macrocyclic heterocyclic unit. Suitable metal ions include sodium, potassium, lithium, copper, zinc or iron ions.
Yet a further possibility for the bridging group R16 is a polysiloxane network polymer where R16 comprises a straight or branched siloxane chain of valency r or a cyclic polysiloxane unit.
Thus compounds of structure (XI) 
where R24, R25, R28 and R29 are as defined above in relation to formula (VII), R32, R33, R34 are R35, are selected from hydrocarbyl such as alkyl and in particular methyl, and each R36 or R37 group is independently selected from hydrocarbyl or a group of formula R6-R30 where R26 and R30 are as defined above in relation to formula (VII), and u is 0 or an integer of 1 or more, for example of from 1 to 20; and (XII). 
where R24, R25, R26, R27, R28, R29, R30 and R31 are as defined above in relation to formula (VII) and R32, R33, R34 and R35 are as defined above in relation to formula (XI). Although formula (XII) has been illustrated with four siloxane units in the ring, it will be appreciated that there may be other numbers of such units in the cyclic ring, for example from 3 to 8, preferably from 3 to 6 siloxane units.
In the above structures (XI) and (XII), it will be appreciated that xe2x80x94Sixe2x80x94 may be replaced by B or Bxe2x88x92; or xe2x80x94Sixe2x80x94Oxe2x80x94 is replaced by xe2x80x94Bxe2x80x94N(R39)xe2x80x94 where R39 is a hydrocarbyl group such as those defined above in relation to group R32 in formula (XI) or a group xe2x80x94R24-R28 as defined in relation to formula (XII) above.
Upon polymerisation, compounds of formula (XI) and (XII) or variants thereof, will form a cross-linked network where the cross-linking occurs through the groups R28, R29, R30 and R31 as illustrated in FIG. 1. Such polymers may exhibit properties similar to those of conventional siloxanes. However, in the case of compounds of formula (XI) and (XII), they may be coated onto surfaces and polymerised in situ, for example using radiation curing.
Further examples of compounds of formula (III) include compounds of formula (XIII) 
where R24, R25, R26, R27, R28, R29, R30 and R31 are as defined above in relation to formula (VIII).
The methodology of the invention may also be applied to the production of liquid crystal polymers. In this case, the monomeric units will include a mesogenic group as is understood in the art.
For example, suitable polymers may be obtained by the polymerisation of compounds of formula (III) where R16 xe2x80x2 comprises a group of sub formula (XIV)
R33xe2x80x94Z6xe2x80x94R24xe2x80x94xe2x80x83xe2x80x83(XIV)
where R24 is as defined above, Z6 is selected from O, S, single covalent bond, COO, OCO; and R33 represents any mesogenic group;
Compounds of this type are novel and form the subject of a copending patent application of the applicants.
Compounds of formula (II) are suitably prepared by conventional methods, for example by reacting a compound of formula (XV) 
where X1, Y1, Y2, R2, R2, R3, R4, R5 and the dotted bonds are as defined in relation to formula (II), R1xe2x80x2 is a group R1 as defined in formula II or a precursor thereof, and R40 is hydrogen or hydroxy, with a compound of formula (XVI)
R16xe2x80x94[R6xe2x80x94Z4]rxe2x80x83xe2x80x83(XVI)
where R6, R16 and r are as defined in relation to formula (II) and Z4 is a leaving group, and thereafter if necessary, converting a precursor group R1xe2x80x2 to a group R1.
Where a compound of formula (IIA) is produced, the compound of formula (XV) will be of formula (XVA) 
where R1xe2x80x2, R2, R3, R4, R5, R40, X2, X3, Y2 and Y3 are as defined above.
Suitable leaving groups Z4 include halogen in particular bromo, mesylate or tosylate. The reaction is suitably effected in an organic solvent such as tetrahydrofuran, dichloromethane, toluene, an alcohol such as methanol or ethanol, or a ketone such as butanone and at elevated temperatures for example near the boiling point of the solvent.
Preferably the reaction is effected in the presence of a base such as potassium carbonate.
When the group R1xe2x80x2 is a precursor of the group R1, it may be converted to the corresponding R1 group using conventional techniques. For example R1xe2x80x2 may be a nitrogen atom, which may be converted to a group NR12 (Zmxe2x88x92)1/m where R12, Z and m are as defined above, by reaction with an appropriate salt under conventional conditions. Examples of this are illustrated hereinafter.
Compounds of formulae (XV) and (XVI) are either known compounds or they can be prepared from known compounds by conventional methods.
During the polymerisation process, the compounds link together by way of the multiple bond, in particular the diene group as illustrated in FIG. 1. Where the compounds used include more than one diene grouping, for example compounds of formula (II) where R is 2 or more, they will tend to become cross linked to form a network or three dimensional structure. The degree of cross linking can be controlled by carrying out the polymerisation in the presence of cross-linkers, where for example r is greater than 2, for example 4, or diluents. The latter will suitably comprise a compound of formula (XVI) 
where X1, X2, Y1, Y2, R1, R2, R3, R4, R5, R6, R16 and r are as defined in relation to formula (II).
The method of the invention can be used in the preparation of homopolymers or copolymers where they are mixed with other monomeric units, which may themselves be of a similar basic structure, for example of formula (II) or otherwise.
A general scheme illustrating the sort of polymerisation process which may occur using a polyethylene type bridging group is illustrated in FIG. 2.
Using the method of the invention, it is possible to take a suitable organic system that has optimal or optimised properties for use in certain applications, e.g. high yield strength, large hyperpolarisability, high pyroelectric coefficient, high conductivity etc. and to structurally modify the system so that it is possible to polymerise it. If functional groups are incorporated that will polymerise, it will become possible to create a three dimensional network or plastic that will have properties associated with the parent organic system.
The advantages of the compounds of the invention is that they allow for the possibility that they can be applied in the form of a paint and caused to polymerise in situ. Thus this allows for ease of processing. Further, by providing for the construction of networks as a result of the cross linking, the resultant polymer can be mechanically strong and durable.
The versatility of the systems of the invention mean that it is possible to build in anisotropy which would improve directional physical properties, e.g. NLO, mechanical yield strength etc. Both amorphous or ordered systems can be prepared depending upon the particular polymerisation conditions used.
Copolymerisation is also possible and this can be used advantageously to affect physical properties of the polymer obtained.
Polymers obtained using the method of the invention maybe particularly suitable for the production of adhesive coatings, and multilayer coatings as well as binders. It is possible to manipulate the low molar mass coating before polymerisation is carried out, e.g., poling etc.
Films of polymeric material can be prepared as illustrated hereinafter. Thus material with the properties of for example, polyethylene films can be produced using radiation curing techniques if required.
Polymer coatings prepared as described herein have useful water-proofing, corrosion resistance and general dust and dirt protective properties, in particular where they include halogenated and particularly fluorinated bridging groups. Thus they may be used in the production of fabrics such as clothing, electrical components or devices, mechanical components as well as building materials which require this feature. In addition, coatings of this type may produce anti-icing features which are useful, particularly where these materials are exposed to harsh external conditions. Products treated in this way also exhibit strong pearling qualities and this assists in the rapid shedding of condensate. Thus surfaces remain relatively free of such condensates.
Such surfaces can be achieved on at least part of the internal surfaces of a structure containing interconnecting interstitial spaces, such as fibrous or granular material. The present invention provides a product selected from a fabric, an electrical component or device, a mechanical component, or a construction or building material, having deposited thereon a polymeric coating derived from a monomer of formula (I) as defined above.
Suitable electrical components include small electrical components such as resistors, capacitors, condensers, circuit breakers, switches and connectors, as well as small assemblies of these, for example circuit boards on which these and/or other components are mounted. Electrical devices include conductors, such as HT leads for example, those used in automobile engines, and cables such as external or underground power cables. Such cables may be pre-coated with plastics of another insulating material.
Plastics coatings in accordance with the invention may be applied to electrical wiring. In particular, monomers of formula (I) which mimic polypropylene would be useful in this context.
Mechanical components include housings, bearings, shafts, gears, wheels, gaskets, filter housing, engines, gearboxes, transmission, steering or suspension components.
Building materials include wood, brick, concrete slabs or other pre-formed concrete structures, building blocks, stone, slates or insulation materials where there is a possibility that corrosion, weathering or water penetration is likely to cause problems.
Polymer coatings formed in accordance with the invention may be useful in electronic components which have a polymeric coating as resistance layers. The nature of the bridging group R16 will affect the resistance of the polymer layer.
Optionally the bridging groups in the monomers may be aromatic or heteroaromatic, i.e. it may include one or more unsaturated carbon rings, optionally containing heteroatoms such as nitrogen, oxygen or sulphur, which give the surface formed additional resistance to etching by plasma etch processes as used in the semiconductor integrated circuit industry.
If necessary, the coating may be discontinuous, for example, patterned by etching, optionally after masking certain areas, so as to provide the desired electronic properties. Techniques for achieving this are well known, and include for example, irradiation with high energy radiation such as electron beams, X-rays or deep ultraviolet rays.
The irradiation breaks the bonds in the polymer and exposed areas can then be dissolved in a developer liquid. Optionally, the coating may consist of a mixture of a monomer and a chemical designed to enhance its sensitivity to radiation exposure during the patterning process, such as quinione diazide or anthraquinone.
Suitable electronic components include printed circuit boards, semiconductor elements, optical devices, videodiscs, compact discs, floppy discs and the like.